Emulsion type drawing compounds containing carboxyalkyl cellulose salts



United States Patent EMULSION TYPE DRAWING COMPOUNDS CON- TAlNlNGCARBOXYALKYL CELLULOSE SALTS HarryT-Roden, Port Nec'hes, 'Tex., assignorto The Texas Company, New York, N. Y., a corporation of Delaware NoDrawing. Application June 8,1951, Serial No. 230,710

'13 Claims. '(Cl. 252-18) This inyentionrelates to lubricants for metalworking processes. ,More particularly it relates to lubricants of theemulsion type containing a solid tiller and a water soluble salt-ofcarboxyalkyl cellulose.

In metal working processes such as drawing, rolling, pms FP Q SmE, .itisnec ss ry t mplo alub cant .to seduce thefnctiqn be w en the sl d nmetal ,surfaces {to prevent .stickin and scoring of thewwork andexcessive --.w.ear.-on the ie. ;In order to .efiectiyely separate -.th e;metal.;-s urfiaces under the high pressures em ploy dan such proc s s,i i rusual yn c s ry to. e 11103 lubricants -,co,ntaining .inert,fillers such .asflgraphite, talc, bentomte, chalk, .etc. These inertmaterials are \usuallyapplied-to the surface of ,the workin th form .ofasuspension inaliquid carrier, suchas water, a light minerahoilqoreanemnlsion.

.The emulsion-type lubricant containing an inert filler is the; most;generallysatiefactory lubricant for cold ,metal itonnmeap cesscs, (s ncy reas n of in both i y d sohd snspension ingredients it serves .as .a.kdouble-functioning lubricant, and in addition is easily remoyed after:;use bywashing'ewith watenor-With. analkali solution. For

:.the sake of convenience randieconomy, lubricantsof this type :areordinarily prepared "by :themanufacturer in the :consistency of a softgrease concentratehaving the S lid --fil.en.d1s;persed therein and;containing only a small, amount of; Water suflicient @to form a stablecomposition. This concentrate is then further diluted with water in vthe-Shop .to the :desired concentration of lubricant accord.

'ingwtothe;specificmequirements. of the operation in which ,itdsitobeemployed. v

while-a numberiof different compositions-of thea-bove type whiclrihave;been. employed heretoforetin metal .workng operations ;have;ag-iyensatisfactory .lubrication .in rela- ;t1vely -.concent rated form, as forexample in -,a dilution 'rat-ioof: 1 (0 E1- or less, 1 theysare:-generallyunsatisfactory at gh-igher idilutions, schiefly -;beca,us.e ,the emulsions thus ,producedhave-insufiicient viscosityandadhesiveness tonietal to form lubricating films-.oftthe .necessarythickness upon .the surface-ofwthe work. Another difficultyis thattheremulsionfbreaks down ,either on standingor in useso that --an.-o.i.o.-fihnrwhich cannot be removedbywashing with another difficulty isthat the particles ofjfiller material tend to separate and sediment whenthe emulsionfis pers-mitted-togstand'iimdilutediform.

zstn. accordance-:Wi-tb-nnyyention, fan improved ;lnbri-.1oating;;composition :for zthetzcold forming of -meta-ls. com-:prisessan r aqueousemulsion of .-:a mineral lubricating :Qi containingasolid :filler and a small amount of a water soluble salt-ofacarboxyalkyl cellulose. M-y.-..preferr ed composition is/an'aqueousemulsion ofa mineral'lubricating oil-containing aifatty acidsoap as an-;emulsif-yi ng agent and'a solidfillercomprising in major proportion.calciumca'rbonate in'finely *dividedform 'The'composition ispre'ferably. siighftly alkaline with a small-amount of free alkali.

l ica ing;c mp n .cf. .thelah rcmcompos ion f mco hw dh nt. thick.filmsup nmeta .surtace when employe v in either. concentr ed -.or.. ilutQ m' "the :emulsify, readily with .Water andiform uniform and{emulsions-of goodyisces-ity tBIid'JQ h-Q d sir b 1 :characteristicsoveni-aawide range of ehaidasennifcrmn t iorlys ouiponent.

ice

erties do not deteriorate upon standing by loss of emulsion or bysettling fontof the solid particles.

The water soluble salts of carboxya'lkyl cellulose employed are chieflyalkali metal or alkaline earth metal 5 salts of cellulose derivatives in.Which a portion of thehydroxy groups are ether-ified withcarboxy-containing aliphatic groups. As examples .of such compoundswhich may be mentioned are sodium carboxymethyl cellulose, ammoniumcarboxyethyl cellulose, calcium carboxypropyl cellulose and potassiumcarboxyhexyl cellulose. The preferred compound of this ,class is sodiumcarboxyrne'thyl cellulose, which may be readily obtained in the knownmanner by dissolving cellulose fibers in sodium hydroxide solution toaccomplish some degradation in lthe molecular chain length and to formsodiiim cellulose, which is then treated with monochloracetic acid. Inorder to obtain a water soluble product, the'proce'ss is carried out insuch a manner {that at least about :10 per cent and preferably about 13per cent of thehydroxy groups are .etherified.

A number of products of this character areavailable commercial-ly, aparticularly suitable product being .the'water soluble sodiumcarboxymethyl cellulose sold by the Drilling Specialties Co, Bartlesville, Oklahoma, under the trade name of Driscose. This has been employedextensiyely-as a drilling mud additive. i

The carboxyalkyl cellulosesalts may be present in extremelysmallarnounts, such as 0.05 per cent or less, or in amounts above 1 percentWhe're-the compositions are to'be diluted with water in highdilution ratios such as 1:3 ;or higher. For {most purposes they areemployed i i-amounts betweenabout 0.1 and l.pe r cent,.and.pre ferablyfrom about 0,2 to 0.5 per cent by Weight based o'nflthe weight of theundiluted composition.

"The emulsifying agentemployed in these compositions is preferably analkali metal fatty acid soap, obtained by saponifying a fat of animal,jyegetable or synthetic origin with tan :alkali metal hydroxide or othercompound.

A particularly suitable soap' is the sodium soap of Wool fat. inadditionto-the fat'tyacid soap other emulsifying 40 agents may beemployed such as petroleumsulfonates.

The "lubricating oil component may be any suitable medium viscosityfraction from a paraffinic, naphthenic or mixed base crude, obtained bysimple distillation or by any of the usualrefini-ng-methodssuchassolvent-treating,

4.5 acid treating, etc. It is preferably a distillate oil fraction from-a naphthenic base crude {raving an SUS viscosity atlOO" ---F.'"in therange from about 275 to about 325.

The solid filler is preferably calcium carbonate or calcium carbonatemixed with'a-minor amount of a different soli gsuch as tflg "oystershellorclays of various .tynes- (Eli calc um ce bcnatam y b bt n y ginding 1 a natural {material i such as chalk. to suitable particle s z cma b qrr a c 'ehs c l Az e ip t ca ciu eca bona is p ef rably ed, hav na pa t cle bstantially below -about-325 mesh but not ,rnore than ab 4 thi ;-.c

- 10 :micr

cha c r.

Julonf czthcr mponsat recite a v at ewmpositioninay also ontaimminoramounts .of .otherrnate al c e yp 'c ti r n emp o e n l i .Minecompositions-of -,this ;ch aracter such as anti foarn, agents, extrem pe u a ent ucha st u tcon a n c mpound materi i m qccmp u s 5 :0 mp ve Xth app .ance oro'dorLnfthe composi on. .and \SOxfQIllh.

gin concentrated form, the lubricating remulsions of this invention maycornprise about 110. to per cent 1 by weight of solid filler cornprising,in major proportion larly uit able materiali [of this all Ae t e easmen 70 calcium .11' Q a o t .0 pe c n by W h atty-.-acid,soapcontainingia small amount of .free :BJE IQlltfOJ -;to lpercentormore by .we ghLof ,alkali,

a Wat l0 --Wetc an th 19b I1 medium viscosity.

Composit ons of fil hau ed? t ,by .yyeight .of particles .beloyv.

eisoluble; salt,. ofearboxyalkyl; cellulose, about 0.5

about 0.1 to 0.5 per cent by weight of sodium carboxymethyl cellulose,about 1 to 5 per cent of water and a naphthene base lubricating oilhaving an SUS viscosity at 100 F. of about 275 to 325. For more severe dawing operations the emulsion preferably contains about 32 to 38 percent by weight of calcium carbonate, about to 16 per cent by weight ofthe fatty acid soap and about 0.1 to 0.5 per cent by weight of sodiumcarboxymethyl cellulose. For deep drawing operations, the emulsionpreferably contains about 52 to 5 8 per cent by weight of calciumcarbonate, about 8 to 14 per cent by weight of the fatty acid soap andabout 0.2 to 1 per cent by weight of sodium carboxymethyl cellulose.

The above compositions may be used directly in the form of a paste byspreading them over the surface of the metal to be pressed, rolled orotherwise shaped, or they may be diluted with water to form free-flowingemulsions. For example, they may be diluted with water in a dilutionratio of l to l or higher, such as in a dilution ratio 1 to 2 or even 1to 3 in some cases.

The emulsion may be made up by conventional procedures. For example, afat such as tallow, palm oil, degras or other suitable saponifiablematerial may be saponified with an alkaline solution such as sodium orpotassium hydroxide, and the oil, filler, water and carboxyalkylcellulose salt worked in gradually.

According to my preferred method for preparing these lubricatingcompounds, the saponification is carried out at 2903l0 F. employing asmall excess of alkali, amounting to from about 0.1 to about 0.5 percent excess based on the weight of the finished product as calculatedfrom the saponification number of the fat, and in the presence of aportion of the oil which forms the oil phase in the final product.Following the saponification, the mixture is maintained at thistemperature until the soap is dehydrated and the remainder of themineral oil added with stirring. The calcium carbonate is then addedslowly with continued stirring at a temperature of 260-280 F. When thetemperature has dropped below about l90200 F., an odorant material,water and carboxyalkvl cellulose salt are added and the mix cooled tol05-ll0 F. with continued stirring until the compound is uniform and ofa soft buttery consistency of about 300 penetration at 77 F. The productis drawn atl 513111; temperature and is not reheated in excess of Thefollowing example is given to illustrate the preparation of a typicalcompound of my invention and to demonstrate its superior properties ascompared with a drawing compound of the usual type employed at thepresent time.

EXAMPLE A ch arge comprising 950 pounds of degras having asaponification number of 120, 182 pounds of naphthene base lubricatingoil having an SUS viscosity at 100 F. of 300, 400 pounds of water, and182.5 pounds of a 49 per cent solution of caustic soda, corresponding toan excess of 0.1 per cent of alkali based on the weight of the finishedproduct, was introduced into a steam heated kettle and heated withstirring for 2 to 3 hours at 290 F. to acconiplish saponification anddehydration. The materiatwas then maintained at this temperature for anadditional 3 hours while 3704 pounds of the naphthene base lubricatingoil was worked in slowly. The heating was then discontinued and 2700pounds of S wansdown calcium carbonate added gradually with stirring. Inorder to improve the odor of the composition 25 pounds of pine tar wasadded also, when the temperature had dropped below 200 F. With continuedstirring, 194 pounds of water was next added gradually during 1 hourwhile the temperature was maintained at 190 F., and finally 16 pounds ofDriscose in admixture with 100 pounds of the calcium carbonate while thetemperature was about 140 F. The stirring was continued for two hoursafter the "Driscose was added, and the batch finally drawn at 105 F.

The product obtained by the procedure described above was a soft paste,light brown in color and of a smooth, non-grainy texture, having apenetration at 77 F. of 331. The test results given in the followingtable show the improved coverage and adhesion properties of thiscompound in comparison with those of an emulsion type lubricant of theusual composition. of the table is that described above. Lubricant No. lwas prepared with the same lubricating oil base and Lubricant No. 2

with the same soap, but with a dilferent type of filler and without thesodium carboxymethyl cellulose.

Table Lubricant N0 a 1 Comoosltion, percent by weight:

Sidinm soup of degr'ts Lubricating oil Calcium cerbona Talc Pine tarTests:

Emulsifiability Viscosity, 77F., cps. 1:1 dilution After 24 hours Filmweight, gm./sq. in., 1:1 diluti0n Sedimentation at 77 F., 1:2 di1utiouAfter 24 hours After 7 days After 14 days Visibile sedimentation.

The viscosity values in centipoises given in the above table wereobtained by means of the Brookfield Synchro Electric Viscometer uponsamples which were prepared by mixing together grams of the testmaterial with 100 grams of distilled water at 77 F. until uniform.

The film weight values of the table were obtained in the followingmanner: A thin piece of polished steel plate, about 1.75 inches by 4inches by 0.05 inch thick was weighed to the nearest 0.1 gram andimmersed 2 inches into a beaker of the compound diluted one to one withdistilled water and at a temperature of 77 Ir. After a few seconds itwas removed, drained in a vertical position for one minute andreweighed. The weight of diluted compound retained on the plate wascalculated from the increase in weight and the square inches 01 immersedsurface.

The sedimentation test of the table was carried out by graduallydiluting a 100 gram sample of the test compound with 200 grams ofdistilled water and permitting the diluted compound to stand in astoppered graduate for 2 weeks at 77 F. At the end of the indicatedperiods the amount of sedimentation was observed.

The results given in the above table show the outstandingly superioradhesive and coverage properties of a typical compound of my inventionover those of an emulsion type lubricant of conventional composition.These superior lubricating properties are strikingly demonstrated by theincrease film weight obtained with my compound, amounting to over 10times that obtained with the known compound. In addition, nosedimentation of filler occurred after 14 days with my compound in a 1:2dilution with water, whereas in the case of the other compoundsedimentation took place within 24 hours.

Obviously many modifications and variations of the invention, ashereinbefore set forth, may be made without departing from the spiritand scope thereof, and therefore only such limitations should be imposedas are indicated in the appended claims.

I claim:

1. An improved lubricating composition for metal working which consistsessentially of an aqueous emulsion of a naphthene base lubricating oilhaving an SUS viscosity at 100 F. of about 275 to 325, containing about5 to 20 per cent by weight based on the weight of the composition of asoap obtained by saponifying wool grease with a small excess of alkali,about 10 to 70 per cent by weight based on the weight of the compositionof finely divided calcium carbonate, about 0.1 to 1 per cent by weightbased on the weight of the composition of sodium carboxymethylcellulose, and about 0.5 to 10 per cent by weight based on the weight ofthe composition of water.

2. An improved lubricating composition for metal working which consistsessentially of an aqueous emulsion of a naphthene base lubricating oilhaving an SUS viscosity at 100 F. of about 275 to 325, containing about12 to 18 per cent by weight based on the weight of the composition of asoap obtained by saponifying wool greasewith a small excess of alkali,about 15 to 20 per cent by weight based on the weight of the compositionof calcium carbonate having a particle size below about 325 mesh, about0.1 to 0.5 per cent by weight based on the weight of the composition ofsodium carboxymethyl cellulose, and about 1 to 5 per cent by weightbased on the weight of the composition of water.

3. An improved lubricating composition for metal working which consistsessentially of an aqueous emulsion of a naphthene base lubricating oilhaving an SUS viscosity at 100 F. of about 275 to 325, containing aboutto 16 per cent by weight based on the weight of the composition of asoap obtained by saponifying wool grease with a small excess of alkali,about 32 to 3.8 per cent by Weight based on the weight of thecomposition of calcium carbonate having a particle size below about 325mesh, about 0.1 to 0.5 per cent by weight based on the weight of thecomposition of sodium carboxymethyl cellulose, and about 1 to 5 per centby weight based on the weight of the composition of water.

4. An improved lubricating composition for metal working which consistsessentially of an aqueous emulsion of a naphthene base lubricating oilhaving an SUS viscosity at 100'F. of about 275 to 325, containing about8 to 14 per cent by weight based on the weight of the composition of asoap obtained by saponifying wool grease with a small excess of alkali,about 52 to 58 per cent by weight based on the weight of the compositionof calcium carbonate having a particle size below about 325 mesh, about0.2 to 1 per cent by weight based on the weight of the composition ofsodium carboxymethyl cellulose, and about 1 to 5 per cent by weightbased on the weight of the composition of water.

5. Claim 1 wherein the lubricating composition is diluted with water ina dilution ratio of from about 1:1 up to about 1:3.

6. An improved lubricating composition for cold metal working whichconsists essentially of an aqueous emulsion of a mineral lubricatingoil, containing about 10 to 70 per cent by weight based on the weight ofthe composition of calcium carbonate in finely divided form, about 5 toper cent by weight based on the weight of the composition of an alkalimetal soap, about 0.1 to

1 per cent by weight based on the weight of the com- -1 position of awater soluble salt of carboxyalkyl cellulose wherein the alkyl groupcontains from 1 to 6 carbon atoms, and about 0.5 to 10 per cent byweight based on the weight of the composition of water, said compositionbeing free from excess fatty acid and slightly alkaline with a smallamount of free alkali metal hydroxide.

7. An improved lubricating composition for cold metal working whichconsists essentially of an aqueous emulsion of a mineral lubricatingoil, containing about 10 to per cent by weight based on the weight ofthe composition of calcium carbonate in finely divided form, about 5 to20 per cent by weight based on the weight of the composition of analkali metal soap, about 0.1 to l per cent by weight based on the weightof the composition of a water soluble salt of carboxymethyl cellulose,and about 0.5 to 10 per cent by weight based on the weight of thecomposition of water, said composition being free from excess fatty acidand containing about 6 0.05-0.5 per cent by weight of free alkali metalhydroxide.

8. A lubricating composition according to claim 7 in which the watersoluble salt of carboxymethyl cellulose is sodium carboxymethylcellulose.

9. A lubricating composition according to claim 7 in which the soap isan alkali metal soap obtained by saponifying wool grease.

10. A lubricating composition according to claim 7 in which the minerallubricating oil is a naphthene base lubricating oil having an SUSviscosity at F. of about 275 to 325.

11. An improved lubricating composition for metal working which consistsessentially of an aqueous emulsion of a mineral lubricating oil,containing about 5 to 20 per cent by weight based on the weight of thecomposition of an alkali metal fatty acid soap, about 10 to 70 per centby weight based on the weight of the composition of an inert finelydivided filler, about 0.1 to 1 per cent by weight based on the weight ofthe composition of a water soluble salt of carboxyalkyl cellulosewherein the alkyl group contains from 1 to 6 carbon atoms, and about 0.5to 10 per cent by Weight based on the weight of the composition ofwater, said inert filler being selected from the group consisting offinely divided calcium carbonate, and a major proportion of finelydivided calcium carbonate mixed with a minor amount of another inertfiller selected from the group consisting of talc, oyster shell andclay.

12. Claim 11 wherein the lubricating composition is diluted with waterin a dilution ratio of from about 1:1 up to about 1:3.

13. An improved lubricating composition for metal working which consistsessentially of an aqueous emulsion of a mineral lubricating oil,containing about 5 to 20 per cent by weight based on the weight of thecomposition of an alkali metal fatty acid soap, about 10 to 70 per centby weight based on the weight of the composition of finely dividedcalcium carbonate, about 0.1 to 1 per cent by weight based on the weightof the composition of a water soluble salt of carboxyalkyl cellulosewherein the alkyl group contains from 1 to 6 carbon atoms, and about 0.5to 10 per cent by weight based on the weight of the composition ofwater.

References Cited in the file of this patent UNITED STATES PATENTS NumberName Date 1,409,658 Brann Mar. 14, 1922 1,449,379 Bullock Mar. 27, 19231,617,455 Montgomery Feb. 15, 1927 2,003,564 Thorpe June 4, 19352,112,632 Montgomery Mar. 29, 1938 OTHER REFERENCESCarboxymethylcelluloseUses and Applications, Hollabaugh et al., Ind. andEng. Chem., Oct. 1945, vol. 37, No. 10, pages 943-947. (Copy in Div.64.)

1. AN IMPROVED LUBRICATING COMPOSITION FOR METAL WORKING WHICH CONSISTSESSENTIALLY OF AN AQUEOUS EMULSION OF A NAPHTHENE BASE LUBRICATING OILHAVING AN SUS VISCOSITY AT 100* F. OF ABOUT 275 TO 325, CONTAINING ABOUT5 TO 20 PER CENT BY WEIGHT BASED ON THE WEIGHT OF THE COMPOSITION OF ASOAP OBTAINED BY SAPONIFYING WOOL GREASE WITH A SMALL EXCESS OF ALKALI,ABOUT 10 TO 70 PER CENT BY WEIGHT BASED ON THE WEIGHT OF THE COMPOSITIONOF FINELY DIVIDED CALCIUM CARBONATE, ABOUT 0.1 TO 1 PER CENT BY WEIGHTBASED ON THE WEIGHT OF THE COMPOSITION OF SODIUM CARBOXYMETHYLCELLULOSE, AND ABOUT 0.5 TO 10 PER CENT BY WEIGHT BASED ON THE WEIGHT OFTHE COMPOSITION OF WATER.